Beta-arylated naphthoxidines and a method of preparation



United States Patent 3,539,597 B-ARYLATED NAPHTHOXIDINES AND A METHOD OF PREPARATION Hans Bosshard, Basel, and Werner Bossard, Riehen, Switzerland, assignors, by mesne assignments, to H. A. Whitten & Co., New York, N.Y., a partnership No Drawing. Original application Jan. 19, 1966, Ser. No. 521,492, now Patent No. 3,338,659, dated Aug. 29, 1967. Divided and this application May 8, 1967, Ser. No. 645,089 Claims priority, application Switzerland, Nov. 15, 1961, 13,244/ 61 Int. Cl. C07c 49/66, 87/64 US. Cl. 260-396 21 Claims ABSTRACT OF THE DISCLOSURE Arylated naphthoxidines are produced by reacting a naphthoxidine of the formula wherein each X represents hydrogen, chlorine, bromine, lower alkyl or phenylamino, at least one X being hydrogen and not more than one X being phenylamino with, per mol thereof, at least one mol of a diazonium salt of the formula wherein A' is an anion and R is the radical of a monoto bicyclic aromatic compound. According to the invention, end products having a further substituted naphthalene radical can be obtained by converting by reduction and/ or oxidation, fisubstituted, in particular halogenated naphthalene compounds having suitable substituents in at least two fi-positions, into naphthoxidines and then reacting these with diazonium compounds. The arylated naphthoxidines are useful in the dyeing of hydrophobic textile materials.

This application is a division of application Ser. No. 521,492, filed Jan. 19, 1966, now US. Pat. 3,338,659, which is in turn a continuation-in-part application of our copending applications Ser. No. 327,100, filed Nov. 29, 1963 and No. 440,918, filed Mar. 18, 1965 (both of which are now abandoned) which are in turn continuation-in-part applications of our patent application Ser. Nos. 237,755 and 237,760, both filed Nov. 14, 1962, the latter applications now being abandoned.

The invention concerns in a first aspect a process for the production of new naphthoxidines which are arylated at the central naphthalene ring, new compounds of the latter type and their use for the dyeing of textile fibers. It also concerns partcularly hydrophobic textile materials dyed with the new arylated naphthoxidines.

3,539,597 Patented Nov. 10, 1970 It has been found that new valuable arylated naphthoxidines are obtained by reacting compounds of the formula wherein each X represents independently from the others hydrogen, chlorine, bromine, lower alkyl or phenylamino, at least one X being hydrogen and not more than one X being phenylamino, with aromatic diazonium compounds, the resulting novel compounds, derivatives of the compounds of Formula I which are resonance hybrids, of which Formula I covers the limit electron configurations, as described by Ernest Merian in Chemie der Aminonaphthochinone (Chimia, 13, pages 181-212, (1959), and are referred to in this specification and the appended claims for the sake of brevity as naphthoxidines. The compounds of Formula I may be further substituted at the naphthalene nucleus or at one of the nitrogen atoms and, moreover, one to three of the hydrogen atoms bound to the naphthalene nucleus, can be substituted as follows:

Naphthoxidines which are usable as starting materials in the process according to the invention can be further substituted at the napthalene nucleus in the 2-, 3-, 6- or 7-position and at the nitrogen atoms linked to the 1- or 5-position. Halogen atoms such as fluorine, chlorine or, preferably, bromine, lower alkyl groups such as methyl,- ethyl, n-propyl, isopropyl groups and secondary or tertiary amino groups such as, e.g. phenylamino or N-lower alkyl-N-phenylamino groups can be present as substituents of the naphthalene nucleus. Substituents of the nitrogen atoms in the 1- and S-position of the naphthalene ring can be hydrocarbon radicals which may be further substituted such as by lower alkyl or aryl groups, in particular phenyl, bromophenyl, chlorophenyl, lower alkylphenyl, and lower alkoxyphenyl groups.

The substitution of a free hydrogen atom, bound to the naphthalene nucleus of naphthoxidine, by the radicals of a diazonium salt with cleavage at the nitrogen of the group of the latter is very unexpected, for naphthalene derivatives such as 1-hydroxy-4-amino-naphthalene couple with diazonium salts with formation of an azo bridge N=N.

The naphthoxidines used as starting materials in the process of the invention fail to show the typical qninone reaction of, for instance, benzoor naphthoquinone. Furthermore, the known arylated benzoor naphthoquinones are relatively unstable due to their pronounced quinone character and are unsuited for use as dyestuffs.

Ring substituted arylated iminobenzoquinones and iminonaphthoquinones have never been produced prior to the present invention, to the best of our knowledge.

Aromatic diazonium compounds which are suitable as reactants in the process of the present invention are those of carbocyclic as well as those of heterocyclic, monoor bicyclic radicals which retain their aromatic character even in strongly acid solutions, and are of the formula [REN1A (11) wherein A is a suitable anion such as (31*, N 1 80 HCOO and the like. The nature of the anion is not critical.

R in the above formula is either one of the carbocyclic aromatic radicals with a benzene or a naphthalene nucleus, or one of the heterocyclic aromatic radicals with a ring system which retains its aromatic character even in strongly acid solution and the amino-substituted analog of which, i.e. RNH is diazotizable; R being preferably with a pyridine, quinoline, thiazole, benzothiazole, tetra zole, pyrazole, benzoxazole, thiadiazole, benzimidazole, indazole nucleus.

The carbocyclic or heterocyclic aromatic radicals R can contain one or more further substituents as desired and these may. be ionogenic groups such as, e.g. the carboxyl or the sulfonic acid group or, preferably, non-ionogenic groups,

Examples of non-ionogenic substituents are: hydrocarbon groups such as methyl, ethyl or phenyl groups, ether groups such as methoxy, ethoxy, butoxy or phenoxy, chlorophenoxy, phenylthio groups, in particular, however, also electrophilic substituents which increase the reactivity of the diazonium group such as the nitro, cyano, trifluoromethyl group, azo, keto, carbocyclic acid ester, sulfonic acid ester, sulfonic acid amide, alkylor aryl-sulfonyl groups as well as, preferably the halogens fluorine, chlorine and bromine.

When R is a phenyl radical, this term means in the specification and appended claims the unsubstituted phenyl radical, as Well as phenyl substituted as follows:

(I) Simple substituents (a) with one to five halogen atoms with atomic weight of maximally 80, i.e. chlorine, bromine and/ or fluorine atoms;

(b) with one to three lower alkyl groups of maximally five and preferably one to two carbon atoms;

(c) with one to two alkoxy groups with maximally four carbon atoms;

((1) hydroxylated and halogenated (chlorinated or fluorinated) lower alkyl groups derived from those defined under (b) supra, especially trifluoromethyl, as well as lower alkoxy-alkyl groups having a total of maximally six carbon atoms;

(e) with one to two of the following radicals: nitro,

cyano;

(g) two to three substituents in combination from one or several of the above listed groups;

(II) Carbonic acid ester radicals (a) alkoxycarbonyl with a total of 8 carbon atoms,

(b) cyclohexyloxycarbonyl radicals and (c) benzyloxycarbonyl radicals which are either unsubstituted or substituted with methyl, chlorine, bromine, or nitro;

(d) combination of one substituent of (II) (a), (b) or (c), with one substituent of (I) (a) to (e), and preferably with nitro, one of the two substituents being preferably in 3- and the other in 4-position at the benzene radical of R;

(III) One sulfonic acid phenyl ester radical which is either unsubstituted or substituted with chlorine, bromine, nitro, or alkyl with maximally 5 carbon atoms;

(IV) One sulfone or one ketone radical namely either lower alkyl sulfonyl, or lower alkyl carbonyl, phenyl sulfonyl, chlorophenyl sulfonyl, lower alkyl phenyl sulfonyl, phenyl carbonyl, chlorophenyl carbonyl, or lower alkyl phenyl carbonyl, wherein lower alkyl has maximally four carbon atoms;

(V) One substituent of the formulas R2 CON R2 and R1 SOz-N R2 wherein R is either hydrogen, or alkyl with maximally five carbon atoms, alkoxyalkyl with maximally six carbon atoms or hydroxyalkyl with maximally three carbon atoms, and R is either hydrogen, or alkyl with maximally 5 carbon atoms, alkoxyalkyl with maximally 6 carbon atoms, hydroxyalkyl with maximally 3 carbon atoms, phenyl, lower alkylphenyl, chlorophenyl, and alkoxyphenyl with alkoxy of maximally 4 carbon atoms;

(VI) One sulfonylamino or carbonylamino substituent of the formula NHZR wherein Z is either SO or CO' and R is either alkyl with maximally 4 carbon atoms or phenyl, alkyl phenyl, alkoxy phenyl, chlorophenyl, nitrophenyl, alkyl and alkoxy as substituents of phenyl meaning radicals of one to four carbon atoms,

and when Z is CO-, R, can also be alkoxy with 4 carbon atoms.

(VII) Phenyl, chlorophenyl, nitrophenyl, phenoxy, chlorophenoxy, nitrophenoxy, phenylthio, methylphenylthio, phenylazo, chlorophenylazo, bromophenylazo, lower alkylphenylazo, especially methylphenylazo, nitrophenylazo, hydroxyphenylazo and di-lower alkylaminophenylazo as substituents in the benzene nucleus of R.

(VIII) Combinations of one of substituents selected from the classes III to VII inclusive, with one to two of the substituents, selected from the group (I) (a) to (e).

When R is a naphthyl radical, this means unsubstituted naphthyl as well as naphthyl substituted with preferably one to two of the substituents chlorine, bromine, nitro, E COOH, or sulfonamido or carbonamido as defined under (V) supra.

When R is a heterocyclic radical as described above, the latter can be either unsubstituted or substituted with alkyl with maximally 2 carbon atoms, alkoxy with maximally 4 carbon atoms, nitro, chlorine or bromine.

Suitable carbocyclic aromatic diazonium salts are, for example, those of aminobenzene, 1-amino-2-, -3- or -4- methylbenzene, 1-amino-2,5-, -2,4- or -3,4-dimethylbenzene, 1-amino2-, 3- or -4-chlorobenzene, 1-amino-2-, 3- or 4-bromobenzene, 1-amino-2-, -3- or -4-fluorobenzene, 1amino-2-methyl-4-chlorobenzene, l-amino-2-methoxy- 4 chlorobenzene, 1 amino 2,4-, -2,5- or -3,4 dichlorobenzene, l-amino-2,4-, -2,5- or -3,4-dibromobenzene, 1- amino-2,4,5-trichloroor tribromo-benzene, 1-amino-3, 4,5-trichloroor -tribromo-benzene, 1-amino-4-chloro-3- trifluoro-methylbenzene, 1-amino-2-, 3- or 4-nitrobenzene, lamino-4-methyl-3-nitrobenzene, l-amino-2,5-dimethyl-4-nitrobenzene, 1 amino-Z-methoxy 4 nitrobenzene, 1-arnino-2-chloroor -bromo-4-nitrobenzene, 1- amino-4-chloroor -bromo-2-nitrobenzene, l-amino-2,5- dichloroor dibromo-4-nitrobenzene, 1-amino-2,3,5,6- tetrachloroor -tetrabromo-benzene, 1- or 2-aminonaph thalene, l-amino-S,8-dichloronaphthalene, 1-amino-4- nitronaphthalene, 2 amino 4 chlorodiphenyl ether, 2- amino 4,4 dichlorodiphenyl ether, 3 amino 4 chlorodiphenyl sulfone, 4-arninobe-nzene methylor acetylsulfone, 4-aminobenzene sulfamide, 3-aminobenzenesulfodiethylamide, 4 aminoazobenzene, 1 amino-4-cyanobenzene, 4-amino-3,2-dimethyl-azobenzene.

Suitable heterocyclic diabonium compounds are, for example, diazotized aminopyridines, aminoquinolines, 2- aminothiazoles such as Z-aminothiazoles, 2-amino-5-nitrothiazole, Z-aminobenzothiazole, 2-amino-6-methoxy-, -6-methyl-, -6-chloroor -6-bromo-benzothiazole, 3- amino-tetrazole, 3-aminopyrazole, Z-aminobenzoxazole, 2-amino-thiodiazole (1,3,4), 5-methyl-Z-aminothiodiazole (1,3,4), 5 aminothiodiazole(l,2,4), 2 or -6-aminobenzimidazole, 3- or 6-arninoindazole, 2-(4-aminophenyl)-6- methyl-benzothiazole.

The napthoxidines which may be substituted as defined above, and which are suitable for use in the process according to the invention, are known or can be obtained by methods known per se, for example, from 1,5-dinitronaphthalenes substituted in the 2-, 3-, 6- or 7-position, by partial reduction with sulfur sesquioxide.

In the reaction according to the invention, from one ot two mols or even an excess over the latter amount, but preferably one mol of diazonium compound is caused to react with one mol of the starting naphthoxidine at a temperature within the range of -15 and 50 C., Whereby an equivalent amount of nitrogen is split ofi and the aromatic radical corresponding to the diazonium compound enters at a free [i-position of the naphthalene nucleus.

More than one, and preferably two diazonium salt radicals R can be introduced into the naphthalene nucleus of the starting naphthoxidines, if the radical R is an active, strongly negatively substituted radical with such negative substituents as those of groups (I)(e) and (f), (II), (III), (IV), (V), and also R with two to five of the halogen substitutes of (I) (a) supra.

According to the invention, end products having a further substituted naphthalene radical can be obtained by converting by reduction and/r oxidation, fl-substituted, in particular halogenated naphthalene compounds having suitable substituents in at least two OL-POSItlOIlS into naphthoxidines and then reacting these with diazonium compounds. However, unsubstituted naphthoxidines can also be treated by known methods with electrophilically substituting agents or they can be arylated at the nitrogen atom and then reacted with aryl diazonium compounds. Finally, the novel naphthoxidines arylated at the naphthalene nucleus by reaction with diazonium compounds can also be modified according to the invention, for example they can be electrophilically substituted and, particularly, halogenated at the naphthalene nucleus; they can also be hydrolyzed or arylated at the nitrogen atom.

The conditions for the reaction according to the invention can be modified within wide margins. Both water or aqueous mineral acid as well as inert organic solvents, preferably those having high solu bilizing properties such as dioxan or dimethyl formamide can be used as reaction media. The naphthoxidines can be reacted both in their free form as well as in the form of a metal halide, e.g. metal chloride or metal bromide adduct. Zinc halide adducts, for example the easily isolated zinc chloride double salt of naphthoxidine can be used in an organic solvent; in the preferred method, the aqueous sulfuric acid solution or suspension of the naphthoxidine is used which results from the production of the naphthazarine intermediate product (see Merian supra) in the usual way from 1,5-dinitronaphthalene.

The temperature and duration of the reaction depend to a considerable extent on the nature of the diazonium compound used. Generally, active electrophilically substituted diazonium compounds react considerably more quickly than the less active nucleophilically substituted aryl diazonium compounds. As mentioned above, the reaction takes place in a temperature range between l and 50 C. and higher, but without causing hydrolization of the desired end products and/or materials. The preferred temperature range is from 5 to -f+25 C. and even +30 C. and the average duration of the reaction is about 3 to 24 hours. The reaction medium can be strongly acid to weakly alkaline; an acid medium of a pH smaller than 2 is preferred because of its more general applicability to all starting uaphthoxidines. In a commercially preferred mode the reaction medium should contain at least about 20% by weight of water. It is also possible, in certain cases, to add the diazonium salt which has been isolated by filtration and optionally drying, to the naphthoxidine starting compound which has been at least partly dissolved in water or in a suitable, inert organic solvent.

The diazonium salt may also be added to the, preferably aqueous, naphthoxidine solution or suspension, in the form of the acid aqueous diazotation solution in which the diazonium salt has been produced in situ.

Quaternized derivatives of the compounds of Formula I in which R is a phenyl radical substituted with one of the heterocyclic radicals defined hereinbefore, and especially with a benzothiazole radical, are obtained by carrying out the above-described substitution of the naphthoxidine ring with the corresponding quaternized and diazotized aminophenyl-substituted heterocyclic starting compound.

Quaternization of the latter starting compounds is carried out in a conventional manner and with the usual quaternizing agents such as dimethyl and diethyl sulfate, methyl or ethyl or propyl bromide or iodide, or methyl or ethyl tosylate.

The process according to the invention is further illustrated by the following diagram:

'ngw Diagram Nnphthoxtdtno Naphthoxidtnc pur-noulerly' p-unaubatltutod g-hulogon lubltltuted I biennium alt ttaphghozidino Nephthoxidlm -:\.t at tuted qubutltuted arm a U 1m; R an halogen partial, mydrolysil homi-naphthszarinl g-subaututed'nth R and optionally with halogen Complete hydrolyl ll llaph thezurlno u-aubutituted with R and 03:11.0 rally-with halogen The reaction products are isolated in the usual way and are purified if necessary by recrystallization or chromatographic adsorption. Further substitution, for example by halogenation or hydrolysis, is performed by known methods.

The aryl naphthoxidines according to the invention are black-blue to green-black glittering crystalline substances which, in a finely distributed suitable preparation with dispersing agents, dye cellulose acetate, wool, synthetic polyamides or polyesters, either without or after an op- 7 tional further treatment, eg, halogenation, in violet, blue to green shades.

All of the compounds obtained according to the process of the invention are useful as dyestuffs for a wide variety of textile fibers among which there are especially polyester and cellulose diand triacetate fibers, as well as wool and synthetic polyamide fibers. Dyeings with these compounds are characterized, depending on the nature of the dyed textile material, by good drawing power, and fastness to light, to sublimation, to alkali, to wet treatment, to sea water, and to gas fumes.

Polyester fibers are dyed with aqueous dispersions of dyestuffs according to the invention, advantageously at temperatures of over 100 under pressure. Dyeing can also be performed, however, at the boiling point of the water in the presence of color carriers such as phenylphenol polychlorobenzene compounds or similar auxiliaries.

Cellulose acetate materials which can be dyed with the new naphthoxidine dyestuffs according to the invention are preferably cellulose diacetate and cellulose triacetate fibers and foils; suitable polyester materials for the purposes of the instant invention are, e.g. polymerizates of alkylene-glycol arylene dicarboxylic acid esters, especially diethyleneglycol terephthalate and xylylenediol terephthalate (Terylene; Dacron; Tergal; Trevira; Kodel); suitable polyamide materials are, for instance, hexamethylene adipate polymerizate fibers (nylon), and -caprlac tam polymerizate fibers (Perlon).

The new dyestuffs according to the invention are further characterized by an excellent reserve for cotton. They are, therefore, particularly suited for the dyeing of fiber blends of cotton and other textile materials to which the aryl-naphthoxidine dyes have good affinity.

The reaction products can serve further as intermediate products for the production of other valuable dyestuffs.

Thus, the imino groups in 1- and/or 5-position at the naphthalene nucleus of the arylnaphthoxidines according to the invention can be subsequently substituted in the same manner as described by Merian supra, for example, with phenyl, lower alkoxyphenyl, alkoxyalkoxyphenyl, alkoxyalkoxyalkoxy-phenyl, phenylazophenyl.

A chlorination of the fl-aryl naphthoxidine according to the invention is carried out preferably with sulfuryl chloride, a bromination with elementary bromine; hydrolysis with a preferably acid hydrolyzing agent such as aqueous sulfuric acid yields as a first stage the corresponding B-arylated hemi-naphthazarines of the formula and complete hydrolysis the corresponding B-arylated naphthazarines of the formula wherein R is one of the substituents (I) to (VII) supra and n is at least 1 and preferably not more than 2.

(A) Among the B-arylated naphthoxidines according to the invention, those of the formula wherein n is an integer ranging from 0 to 3,

X is either chlorine, or, preferably, bromine, R is phenyl substituted with from 0 to 5 halogen atoms,

wherein each Y is independently either hydrogen or a halogen atom of an atomic weight of maximally 80, are dyestuffs of very good drawing power on polyester and cellulose acetate, of good sublimation, of pure blue shades, their wet fastness including fastness to alkali, water, perspiration. Of particular importance are the latter fastnesses for dyeings on cellulose diand triacetate, and the fastness to light, and the fastness to sublimation at temperatures of -180 C., for dyeings on polyester fibers, obtained with the last-mentioned group of compounds according to the invention.

Particularly valuable as dyestuffs or as intermediate products for dyestuffs are the reaction products of nitrobenzene-, dior trichlorobenzene, dior tribromobenzene and of chloro and dichloroor bromoand dibromonitrobenzene diazonium compounds with naphthoxidine.

(B) The dyestuffs according to the invention which have the formula n is an integer ranging from 0 to 3,

X is either chlorine or, preferably, bromine,

R is either alkyl with maximally 6 carbon atoms, or cyclohexyl, benzyl, methylbenzyl, chlorobenzyl, bromobenzyl or nitrobenzyl, and

Y is hydrogen or nitro,

are dyestuffs of similar properties as the last-mentioned class, but are of even better fastness to sublimation. Op timal results are obtained with the dyestuffs of Formula VI in which Y is nitro in 4-position and the ester radical is in 3-positi0n, R being preferably alkyl of from 1 to 6 carbon atoms. Blue to green-blue shades are obtained on cellulose diand tri-acetate and polyester fibers.

(C) The compounds according to the invention which have the formulas Z-Ra 3 H" VII and 1 IKIIH R1 ZN/ (X011 6 Rz 11" (VIII) wherein n is an integer ranging from to 3, X, represents either chlorine or, preferably, bromine, Z represents either -CO-- or SO R represents lower alkyl, phenyl, chlorophenyl, or lower alkylphenyl, while, in Formula VIII each of R and R have independently the meaning given supra under (V), are characterized by more hydrophilic properties than the above-described classes of compounds according to the invention, and are, therefore, better suited for the dyeing of wool and synthetic polyamine fibers, while having similar good fastness property against alkaline milling, chlorine and sea water.

(D) The compounds according to the invention which are of the formula wherein n is an integer ranging from 1 to 2,

X, represents either a chlorine or, preferably, a bromine atom,

Y, represents hydrogen, one fluorine atom or from one to two chlorine, or from one to two bromine atoms, and

Y represents chlorine, bromine or preferably nitro,

are dyestuffs which have good drawing power on cellulose acetate and polyester fibers, good fastness to light and sublimation, and fastness to gas fumes, in which latter fastness those excel in which Y represents two chlorine atoms, and Y is also chlorine, i.e. those having three chlorine atoms as substituents of the benzene nucleus.

This group of dyestuifs is further distinguished by their stability in dyeing processes requiring dyeing baths at temperature above 100 C.

The following examples further illustrate the invention. Parts are given therein as parts by weight and the temperatures are in degree Centigrade.

EMMPLE 1 21.8 parts'of 1,5-dinitronaphthalene are reduced in the known manner with sulfur sesquioxide in sulfuric acid to naphthoxidine. The sulfur which precipitates is removed from the solution of the reduction product in sulfuric acid by filtration. The filtrate is then slowly poured into water and ice while stirring well.

The aqueous hydrochloric acid solution of the diazonium compound resulting from diazotization of 17.8 parts of 2,4-dichloroaniline is added dropwise within about 30 minutes to the blue-violet solution or suspension of naphthoxidine obtained as described above. Foaming ensues and nitrogen is split olf. The reaction is completed in about 16 hours at 25 The precipitated crude product is filtered off under suction, washed with water and, to purify the same, it is stirred into about 1000 parts of water and sodium hydroxide solution is added until the pH is about 12 to 13. The suspension is stirred for 2 hours at room temperature and then the precipitate is filtered off. After washing the blue-black residue with water, it is dissolved in 500 parts of boiling ethanol and any undissolved impurities are filtered off from the solution. The alcoholic solution is evaporated to dryness. A glittering, blue-black crystal powder is obtained which melts at 2082l0 with decomposition. iln ethanol it dissolves with an intensive pure reddish-blue color. Its composition corresponds to the formula TABLE I Shade of dyeing with corresponding aryl compound on cellu- No. Armne lose diaeetate (1) Aminobenzene Reddish-blue. (2) 1-amino-4-methylbenzene D0. (3) Lamina-2, 5-dimethylbenzene. Do. (4) 1-amin0-4-chlorobenz ene D 0. (5) l-amino-2-metl1yl-4-chlorobenzene- Do. (6) 1-amino-2-methoxy-4-chlorobenzene. Do. (7) 1-amino-3, 4-dichlorobenzene. Greenish-blue (8) 1-arnino-2, fi dichlorobenzenm Do. (9) 4-aminobenzene sulfamide Do. (10) 3-amino1-N, N-diethyl-sulfamyl benzene. D o. (11) 4-amln0benzene methylsulfone D0. (12) 4-amino-1-methylsulfonyl-benzene- Reddish-blue. (13) l-amino-d-nitrobenzene Greenish-blue. (14) 1-amino-3-nitrobenzene Reddish-blue. (15). l-amino-Znitrobenzene o. (16) I-amino-Z, fi-dimethyll-nitrobenzene (17) 1-amino-2-methoxy-4-nitrobenzene. (18) 1-amino-2-chloro-4-nitrobenzene- (19). 1-amino-2-bromo-4-nitrobenzene- (20) 1-amino-4-chloro-2-uitrobenzene (21). 2-amino-4-chlorodiphenyl ether..." (22) 1-amin0-2, 4-dibromob enzene (23) 1-amin02, 4-difluorobenzene (24) 3-aminopyridine (25) fi-aminoquinoline- D (26) fi-aminoindazole (27) 2-(4-aminophenyl)-6-methy benzth (28) r l-aminonaphthalene Do. (20) 1-amino-4-cyanobenzene Do. (30) l-arrlino-tt-hydroxyethyl-benzene- Reddish-blue. (31) l-amino i-ethoxy-ethyl-benzene- Do. (32) 4-amino-diphenylketone I 1 D0. (33) 4-amino-dipheny1ether Do. (34) 4-amino-diphenyl-thioether Do. (35). 4-amino'benzoie acid amide Greenish-blue. (36). l-amino-4-methyl-carbonyl-benzeneo. (37). Mesidine Reddish blue. (38) l-amino--isopropyl benzene. D0.

EXAMPLE 2 TABLE II Shade of dyeing 21.8 parts of l,5-d1n1tronaphthalene are reduced in with colrrespondsulfuric acid with sulfur sesquiorride to naphthoxidine f $f and the solution is diluted with ice water as described N Amme 1050 dlacetate in Example 1. (1g--. 1-3.1I1i110,2,4-lZllC%1%01Ol1:))B11Z0110 Grciigiish-blue- (2 l-amino- ,fi-trici oro enzcnc.... 0. A solution of the diazonium sulfate from 21 6 parts of (3) Hm},1W2Y3AGmetmchlombemwe 2,4,5-trichloro-l-amlnobenzene 18 added dropwise, within (4).-- Arnino-pcntachlorobenzene Do. 1d If id (5)... l-arn n0-4-ch1pro-3-trifiupromcthylbenzenc... Do. about 1 hour while stirring, to the ice co su UI'IC ac g g g g 7 1-amino- ,6 ie oro-4-nitro cnzenc... 0. aqueous solution of the naphthoxldine. After stirring for (8), Humu0 2y6kdibmmo 4 nm obenzwe DO 18 hOUIS at 10 {0 the crude product, WhlCh has (9)... 2-flJl1i1'iO-4Ag-difiill0l'0-?lpllti11y%feth%f goddislglglue. ees-ue. formed with development of nitrogen, 18 filtered off and i g g f d i jh l (my) B1 m r'n (11 1-aInino-5,8- ich oronaph aene ue-greenpurified as described in E rample 1. A blue black glitte 1 g O2)- 1mmmo 4 mtmnaphtha1sueV n 9 product which dissolved in ethanol with a pure greenlsh- 15 (13)" p i g 4 5.t -ib Green15h-b1ue blue color is obtained. It is obtained in pure form by (14)" l'ammo4(p'tolynsuuonyl'benzene' chromatographic adsorption when it then melts at 196-- EXAMPLE 3 8 on decom osition. Elementar a iialysis corresponds to the formula a f ls'dmltronaphthaflene are reducfa'd y naphthoxldlne 1n the usual way with sulfur sesquioxide in 185 parts of sulfuric acid. Excess sulfur is removed by filtration of the sulfuric acid solution of the reaction product and the filtrate is diluted with 300 parts of ice H while cooling. A diazonium sulfate solution, obtained by diazotisation of 20 parts of Z-nitro-S-aminobenzoic acid- I C1 n-butyl ester, dissolved in 90 parts of concentrated sulfuric acid while cooling, is added dropwise to this dilute solution of the naphthoxidine at a temperature of 15 to 20 within about 4 hours. After stirring for another 3 hours, during which time the nitrogen development de- 1 creases, the reaction mass is diluted with 1500 parts of ice and water. The precipitated crude product is filtered ofif, washed with water, dilute sodium carbonate solution and again with water and dried. A difiicultly soluble, black impurity is removed by extraction with 500 parts r of boiling ethanol. A blue-black glittering dyestufi? is ob- FOund crcent I tained which dissolves in ethanol with an intensivel pure p e y 1 Calculated (percent): C, 52.21; H, 2.36; Cl, 28.94; N, blue color. It is obtained in pure form by recrystalliza- 744, tion or chromatographic adsorption on aluminum oxide,

Dispersed in Water in the usual way, the dyestuif proand it corresponds to the formula duces pure greenish-blue dyeings on acetate silk or polyester fibers. The dyeings are fast to Wet and light. The N 3 drawing power of the dyestuff is remarkably good. I COO-CHz-OHz-CHzCH If in the above example, instead of the diazonium I compound from 21.6 parts of 2,4,5-trichloro-1-amino- NO2 benzene, diazonium compounds from corresponding amounts of the amines given in the following Table II 1 11111 are used and otherwise the same procedure is followed, then blue dyestuffs having similar properties are obtained. H

TABLE III Shade of dyeing of corresponding aryl compound on poly- No Amine ester fibers (1).... 2-nitro-5-amino-benzoic acid methyl ester Green h-blue. (2).--. 2-nitro-5-amino-benzoic acid ethyl ester.-. Do. (3).-.- 2-nitro-5amino-benzoic acid isopropyl ester. D0. (4)-... 2-11itr0-5-amino-benzoic acid n-amyl ester D0. (5)...- 2-nitr0-5amino-benzoic acid cyclohexyl ester D0. (6).... 2-nitr0-5-amino-benzoic acid B-ethoxyethyl ester Do. (7).... l-arnino-2-chloroi-nitro-benzene D0. (8)...- 1-amin0-2-br0mo-4nitro-benzene.. D0. (9)...- l-amino-ebromo-ii-nitro-benzene.. D0. (10)-.. Lamina-2,5-dichloro-i-nitro-benzene Do. (11)... 4-amino-3-nitr0benzene sulfonic acid diethylamide D0. (12).-. l-amino-2,4,5-trichlor0benzene Blue. (13)... 1-amino-2,3,4-trichlorobenzene 0. (14)..- l-amino-4chloro-3-trifluoromethyl-benzene- Greenish-blue. (15)..- 2-nitro-5-amin0-benzoic acid-benzyl ester D0. (16)... 2-nitro-5-amin0-benzoic acid-Z-methylbenzyl ester.. D0. (17)-.. 2-nitro-5-amino-benzoic acid-4-ch1orobenzy1 ester.. Do. (18)... 2-nitro-5-amino-benzoic acid-4-bromobenzyl este D0. (19).-. 2-nitro-5-amino-benzoic acid-4-nitrobenzyl ester. D0. (20)... 4-amino-benzene-1-sulfonic acid monoethylamid D0. (21)..- l-aminobenzene-B-sulionic acid-2-methylphcnyl est Green-blue (22)--. 4amino-az0benzene--.. Do. (23)... 4-aminobenzene-sulfonic a o. (24).-. 4-aminobenzoic acid hexyl ester- Greenish blue (25).-. 4-aminobenzoic acid methyl este Do. (26)--. 4-amino-benz0ic acid B-ethoxyethy D0. (27)... 3-amin0-benzoic acid fl-ethoxyethyl ester...- D0.

13 It dyes cellulose acetate and polyester fibers from a suitable aqueous dispersion in pure blue shades which have good fastness properties, in particular very good fastness to sublimation on polyester material.

14 Similar products are obtained if in the process described in the above example, equivalent amounts of diazo compound of 3,4-dichloro-l-aminobenzene or 2- chloro-4-nitro-l-aminobenzene are used instead of that of 4-nitro-1-aminobenzene.

If in the process described in the above example, a mixture of 200 parts of glacial acetic acid and 70 parts of concentrated hydrochloric acid is used for the diazo- 6 tisation instead of the 90 parts of sulphuric acid, then A Solutlon of p x q 1n sulfuflc aclfi 15 Produced a somewhat higher yield of the same dyestufl? is obtained. from 9- Parts of 1,5jd11'f1tm'naPhtha1ene In the f l If in the above example, with otherwise the same way w1t h sulfur sesquloxlde. 10.0 parts of 2-am1noth cedure, the diazonium compounds from equimolecular 32916, dlssolved 9 P by Yolume of l amounts of the amines given in the above Table III acld are then diazotised w th nitrosyl sulfur c acld at are used, then correspondingly substituted derivatives hav- 5 to the 'f Solutlons Whlle coohng ihg similar properties are obtained well. This mixture is added dropwise w1thm about three hours while stirring well into ice water, allowed to react EXAMPLE 4 for 2 hours and the product which precipitates is filtered 10,4 pal-ts f dib h h idi b i d as 1 off. Undissolved impurities are removed by recrystallizascribed in German Pat. No. 841,314, are dissolved in tion from ethylene glycol monoethyl ether and, in a y 200 parts of dimethyl formamide. The diazonium chlo- State, it is a greell'black glittering Crystalline Powder ride solution from 494 parts of 4-nitr0aniline is added which dissolves in ethylene glycol monoethyl ether With dropwise to the solution within 1 hour at a temperature a P green Colorbetween 0 and 10. Nitrogen is developed. After stirring It corresponds to i116 formula for 6 hours at 5 to 10, the solution is diluted with water, H the product which precipitates is filtered off and washed. It is purified by recrystallization from ethanol. In polar 5 organic solvents the reaction product dissolves with a l green-blue color; the color is considerably more green I I J than that of the starting material. As dispersion dyestuff, s s the new compound dyes synthetic fibers such as cellulose acetate or polyester fibers in very pure green-blue shades NE of good color strength.

Similar dyestuffs are obtained if, in the above example, the reaction components are replaced by equivalent Green, disubstituted derivatives having similar propamounts of the starting materials given in the following erties are obtained if the procedure given in the above Table IV. example is followed by equivalent amounts of the di- TABLE IV Arylated product Naphthoxidine Amine for diazonium shade of dyeing N 0. component component on polyester (1)-. 3,7-dibromo-naphthoxidine 1-amine-2A-dichlorobenzene Greenish-blue. (2 do 1-an11no 2,4-d1bromobenzene. Do. (3).... 1-amin0-2,4,5-trichlow-benzene" Do. (4) 1-amino2-chloro4-nitro-benzene. Green-blue.

(5) do (6). 3-bromonaphthoxidine. 2-chl0ro-naphth0xidine. 2,6dich10r0-naphth0Xidi 3,7-dibromo-naphthoxidin (12) 2-methyl-naphthoxidine (13). 3-brom0-7-phenylamino-naphthoxidine- (14)-. z methyl-naphtohxidine (15). Z-methyl-naphthoxidine- (16) 3,7-diehloro-naphthoxidine (17) 3-bromo-7-phenylamino-naphth ox (18)- Z-methyl-naphthoxidine (19) 3-bromo-7-phenylamino-naphthoxid (20)- 3,7-dichloro-naphthoxidine l-amin0-2,5-dichloro-4-nitrobenzene 1-amin0-2-ch10ro-4-nitrobenzene 1-amin0-4-nitrobenzene 1-amino-2,4,fi-trichlorobenzene l-amlno-2-bromo-4-nitrob enzene. (10) ..do 3-amino-6-nitrobenzoic acid-n-butylester.. (11) 3-bromo-7-phenylamino-naphthoxidine 1-amino'2-ch1oro-4-nitr0benzene 1-amino-2-fluoro-4mitrobenzene. 1-amin0-2,4,5-trichlor0 benzene l-amino-2,4,5-trichlorobenzene 2-nitro-5-aminobenzoic acid methyl ester- 2-nitro-5-aminobenzoie acid butyl ester- 2-nitro-5-aminobenzoic acid ethyl ester 1-amino-4phenylsulfonyl-benz enel-amino-i methylsultonyl-benzene l-amin0-4-methylsulfony1-benzene o. Greenish-blue.

Green-blue. Do.

.. Greenish-blue.

Green-blue.

. Greenish-blue.

o. Greenish-blue.

EXAMPLE 5 NO "N02 azonium compounds from the heterocyclic amines given in the following Table V are used.

TAB LE V Color of corresponding aryl compound in a glycol monoethyl N0. Heteroeycllc amine ether solution (1) Z-aminobenzthiazole Green. (2) 2-arnino-6-methoxy-benzthiazole D0. (3) 3-aminoindazole Do. (4) Z-amino-E-methyl-thio(Harem-(1,3,4) l Do. (5) 2-amino-5-nitrothiazole Dark green.

EXAMPLE 7 9.3 parts of monocondensation production from naphthoxidine and 1-amino-4-ethoxybenzene according to US. Pat. 2,066,119 are dissolved in dimethyl formamide, 4.94 parts of diazotised 1-amino-4-nitrobenzene are added and the product is isolated as described in Example 4. A green dyestufi is obtained which, in chromatogram, has a difierent Rf value from the starting material.

Similar dyestuffs are obtained by the same method if,

instead of 1-diaz0-4-nitrobenzene, corresponding amounts of 1-diazo-2-chloro-4-nitrobenzene or l-diazo-2,4-dichlorobenzene are used.

EXAMPLE 8 26.8 parts of the end product obtained according to Example 1 are dissolved in 300 parts of chloroform and 15.2 parts of bromine are added. The reaction mixture is refluxed for 2 hours. The solution obtained is Washed neutral with water and the chloroform is distilled off.

The brominated dyestufi, which is obtained in a pure form in the usual Way, e.g. by recrystallizing or absorption on an aluminum oxide column, corresponds to the formula From a suitable aqueous dispersion, it dyes cellulose acetate and polyester fibers in pure blue shades which have very good fastness properties. It has good drawing power.

If in the above example, instead of the 26.8 parts of end product according to Example 1, equivalent amounts of the arylated naphthoxidine in the following Table VI are used, then dyestuifs having similar properties are obtained.

TAB LE VI N 0. Starting material to be brominated F NH O I l I O NH Brommated product shade of dyeing on -H cellulose diacetate (1) R=4-chlorophenyl Reddish blue. (2) R=2,5-dichlorophenyl Do. (3). R =3,4-dichlorophenyl Greenish blue. R =2,4,5-trichlorophenyl Do. R =3,4,5-trichlorophenyl Do. R 2,4-dibrornophenyl- Reddish blue. R=2,5-dibromophenyl 0. R =4-nitrophenyl Greenish blue. R=2-chloro-4-nitropheny Do. R=4-chloro-2-nitrophenyl Do. R=2,5-dichloro-4-nitrophenyl Do. (12)-.- R 2 6-dibromo-4nitrophenyl Do. (13)-.. R=4-ethoxycarbonylphenyL. Reddish blue; (14)- R lnitro-l-naphthyl..- Blue-green. (15)-.- R=2-bromo-4-nitro-phenyl Do. (16) R=2,4 difiuorophenyl- Greenish blue.- (17) R =2-methyl-4-nltro-phenyl- Do. (18) R D 0. (l9) R= Do. (20) R D o. 21; R Do. 22 R= D0.

EXAMPLE 8a If the procedure given in the above example is followed but instead of 15.2 parts, 30.4 parts of bromine are used, then dyestuffs having similar properties and a somewhat more green shade are obtained. Their composition corresponds to the formula:

Chlorine-containing blue dyestulfs are obtained by the above method if the bromine is replaced by the equivalent amount of sulfuryl chloride.

The naphthoxidine dyestuff of the formula EXAMPLE 9 10 parts of the substance obtained according to Table III, No. 7 of the formula 0 NH o are dissolved in 180 parts of 75% aqueous sulfuric acid. The solution is kept for 16 hours at a temperature of 3040 and then diluted with water and ice. The precipitated product is filtered oif, washed neutral and dried. It is obtained in a pure form by recrystallization from chlorobenzene or by chromatographic adsorption on aluminum oxide, and corresponds to the formula The dyestulf dissolves in polar organic solvents with a violet color and it dyes cellulose acetate and polyester fibers from an aqueous dispersion in reddish blue shades.

If the solution in 75% sulfuric acid obtained by the above method is diluted with 500 parts of water and the suspension is heated for 4 hours at 90, then after isolating as described above, a product is obtained which dissolves in pure form by recrystallisation from ethanol and it corresponds to the formula From an aqueous dispersion, the dyestuff dyes cellulose acetate and polyester fibers in red shades.

Dyestuffs having similar shades are obtained, if by the procedure described in the above example, 10 parts of the substance obtained according to Table III No. 12 are used as starting material.

EXAMPLE 10 21.8 parts of 1,5-dinitr0naphthalene are converted according to Example 3 into naphthoxidine, and the filtered sulfuric acid solution thereof is diluted with 1000 parts of ice. Within 3 hours at 20, a diazonium sulfate solution-obtained by diazotizing 18 parts of 4-amino-3,2- dimethylazobenzene in 150 parts of concentrated sulfuric acidis added dropwise to this naphthoxidine solution, 170 parts of water being dropped in at the same time. After another 2 hours stirring at 20, the reaction solution is diluted with 1500 parts of ice and water, the precipitated crude product is separated by filtration, freed from acid by Washing with water, and dried. The product is freed from a low-soluble black contamination by extraction with 500 parts of boiling ethyl acetate. A dyestufi is obtained which dissolves in ethanol with a deep pure green, in 50% sulfuric acid with a deep violet color. It is obtained in its pure form by recrystallization from chlorobenzene and corresponds to the formula Used in a suitable aqueous dispersion, it dyes polyester fibers and cellulose acetate in pure green shades of good fastness properties.

When, in the above example, the diazonium compounds are replaced by equimolecular amounts of the aminobenzenes listed in the following Table VII, the procedure being otherwise the same as before, correspondingly substituted derivatives of similar properties are obtained.

TAB LE VII Shade of dyeing effected with the corresponding aryl com- (12)-.- 4-amino-4-ethylamino-azohenzene Blue-green. (13) 4-amin0-2,4-dirnethyl-azobenzene.. Green. (14). 4-amino-2, 4-d1bron1o-azobenzene- Blue-green.

EXAMPLE 11 2 parts of the dyestuff No. 19 in Table I in Example 1 are dispersed in 4000 parts of water. 12 parts of the sodirurn salt of o-phenylphenol and 12 parts of diammonium phosphate are added to this dispersion. 100 parts of terephthalic acid polyglycol ester yarn are dyed for 1 hours at 95-98". The dyeing is rinsed and after-treated with dilute sodium hydroxide solution and a dispersing agent. In this way a greenish blue dyeing is obtained which is fast to washing, sublimation and light.

If in the above example, the 100 parts of polyester yarn are replaced by 100 parts of cellulose triacetate fabric, dyeing is performed under the conditions given and the dyeing is then rinsed with water, then a blue dyeing is obtained which is distinguished by a high degree of wet and light fastness.

EXAMPLE 12 2 parts of the dyestuff obtained according to Example 3 are finely suspended in 2000 parts of water containing 4 parts of a synthetic dispersing agent in a pressure dyeing apparatus. The pH of the dye bath is adjusted to 6.0 to 6.5 with acetic acid. parts of terephthalic acid polyester fabric are introduced at 50, the bath is heated within 30 minutes to and dyeing is performed for 50 minutes at this temperature. The dyeing is rinsed, soaped and dried. A blue dyeing of pure shade is obtained which is fast to washing, light and very good sublimation.

EXAMPLE l3 2 parts of the dyestuff No. 4 in Table VI of Example 8 are finely suspended in 3000 parts of water containing 6 parts of synthetic dispersing agent. 100 parts of cellulose acetate fabric are introduced at 30-40, the temperature is raised within 30 minutes to 80 and dyeing is performed at this temperature for 50 minutes. The blue dyeing obtained is rinsed and dried. Ithas very good fastness to water, washing and light as well as remarkable fastness to industrial fumes, especially burnt gas fumes.

EXAMPLE 14 A storable dyestuff-dispersant mixture is prepared by intimately mixing by grinding together and subsequently atomizing a mixture of (a) 1 part of the dyestuff No. 7 of Table III prepared according to Example 3, 1 to 3 parts of a synthetic dispersing agent, naphthalene sulfonic acid-formaldehyde condensation product containing the aforesaid components in a ratio of 12:1 by weight,

(b) 1 part of the dyestuff No. 15 of Table VI, prepared according to Example 8a, 1 to 3 parts of lignin sulfonate, sold as Attisol 2,

(c) a mixture of 1 part of the dyestuff No. 9 of Table VI prepared according to Example 8a, 1 part of a synthetic dispersing agent, naphthalene snlfonic acid-formaldehyde condensation product containing the aforesaid components in a ratio of 12:1 by weight, 1 part of lignin sulfonate, sold as Attisol 2.

From the above storable compositions, dyebaths for disperse dyeing of polyester fibers can be prepared by adding water and, if desired, a wetting agent.

EXAMPLE 15 A storable dyestulf-dispersant mixture is prepared by intimately mixing by grinding together and subsequently atomizing a mixture of 1 part of the dyestulf of Example 3,

1 to 3 parts of lignin sulfonate, sold as Attisol 2,

0.01 to 0.5 part of dodecyl benzene sulfonate as wetting agent.

Such storable mixtures as described in Examples 14 and 15 may also be in the form of pastes containing about 1 to 3 parts of water obtained by wet grinding the aforesaid ingredients.

In a similar manner, storable dyestutf dispersant mixtures of equally good properties can be produced with the other dyestuffs described in Examples 1-9.

In a second aspect, the invention concerns new use of new naphthoxidines which are arylated at the central naphthalene ring, new compositions containing as a coloring ingredient naphthoxidines of the last-mentioned type for the dyeing of textile, and particularly of hydrophobic polyester fibers and foils. It also concerns the hydrophobic textile materials dyed with the new arylated naphthoxidines.

In the following portion of this specification, which relates to said second aspect. reference in any example 1 9 to a preceding example means the designated preceding example of this second aspect-portion of the specification.

It is one of the problems in the dyeing of fibers and foils of polyesters, which comprise as used in this specification and in the appended claims, cellulose diand tri-acetate as Well as polyesters in the narrower sense, namely, glycol esters or arylene dicarboxylic acids, especially of the poly-hydroxyethyl terephthalate type, to find dyestuffs which dye these materials with satisfactory drawing power in shades which are fast to light and of at least satisfactory fastness to sublimation; preferably such dyeings on polyester fibers and foils should also be fast to alkali, to wet treatment, to sea water and gas fumes.

The method of dyeing the said polyester materials according to the invention, comprises dyeing of said mate rials preferably from an aqueous dispersion, with dyestuffs which fall under one of the formulas wherein A represents nitro, fluorinated lower alkyl, alkoxy-carbonyl of a total of from 2 to 8 carbon atoms, alkoxyalkoxycarbonyl of a total of from 3 to 8 carbon atoms, cyclohexyloxy carbonyl, benzyloxy-carbonyl, lower alkyl-benzyloxy-carbonyl, chlorobenzyloxy carbonyl, bromo-benzyloxy-carbonyl, nitro-benzyloxy carbonyl, lower alkyl-sulfonyl, N,N-di-(lower alkyl)-sulfamyl, phenylcarbonyl, N,N-di-(lower alkyl)-carbamyl N- phenyl-N-lower alkyl-carbamyl or lower alkanoyl;

A represents hydrogen, chloro, bromo, fluoro, alkyl of l to carbon atoms, or trifluoromethyl;

A represents hydrogen, chloro, bromo, fluoro and alkyl of 1 to 5 carbon atoms;

X represents a member of hydrogen, halogen with an atomic weight of maximally eighty,

m is an integer ranging from 0 to 3 whereby dyeings are obtained which are distinguished by excellent light fastness as well as satisfactory fastness to sublimation.

It is particularly unexpected that those substituents at the phenyl substituent which lead to satisfactory dyeings with naphthoxidines which bear phenyl substituents at one or both imino groups of the naphthoxidine nucleus, for example, the alkoxy substituent in the known compound of the formula 20 Similarly good dyeings on. polyesters as are obtained with dyestutfs of Formula I are also obtained with dyestuffs of the following formula wherein:

0 A represents fluorinated lower alkyl, alkoxycarbonyl of a total of from 1 to 8 carbon atoms, alkoxy-alkoxycarbonyl of a total of from 1 to 8 carbon atoms, cyclohexyloxy-carbonyl, benzyloxy-carbonyl, methyl loweralkyl-benzyloxycarbonyl, chlorobenzyloxy carbonyl, bromobenzyloxycarbonyl, nitrobenzyloxy carbonyl, lower alkylsulfonyl, N,N-di(l0wer alkyl)-sulfamyl, phenylcarbonyl, N,N-di-(lower alkyl)-carbamyl, N- phenyl-N-lower alkylcarbamyl or lower alkanoyl, and m, A and X have the meanings given hereinbefore.

Dyeings with these compounds are characterized, depending on the nature of the dyed textile material, by good drawing power, and fastness to light, to sublimation, to alkali, to wet treatment, to sea water, and to gas fumes.

Polyester fibers are dyed with aqueous dispersions of dyestuffs according to the invention, advantageously at temperatures of over under pressure. Dyeing can also be performed, however, at the boiling point of the water in the presence of color carriers such as phenylphenol, polychlorobenzene compounds or similar auxillanes.

Cellulose acetate materials which can be dyed by the method according to the invention with the neW naphthoxidine dyestuffs by the method of Formula I and II, and those of Formulas III and V described hereinafter, cellulose diacetate and cellulose triacetate fibers and foils; suitable polyester materials for the purposes of the instant invention are, e.g., polymerizates of alkyleneglycol arylene dicarboxylic acids esters, especially di ethylene-glycol terephthalate and hexahydro xylylenediol terephthalate (Terylene; Dacron; Tergal; Trevira; Kodel); suitable polyam-ide materials are, for instance, hexamethylene adipate polymerizate fibers (nylon), and -caprolactam polymerizate fibers (Perlon).

The new dyestuffs used in the new method according to the invention are further characterized by an excellent reserve for cotton. They are, therefore, particularly suited for the dyeing of fiber blends of cotton and other textile materials to which the aryl-naphthoxidine dyes of Formulas I to V have good affinity.

Those compounds of the above Formula I, in which wherein each Y is independently either hydrogen or a 2'1 The compounds which fall under Formula I and are of the formula (III) wherein m is an integer ranging from to 3,

X is either hydrogen, chlorine or, preferably, bromine,

R is either alkyl with maximally 7 carbon atoms, or

cyclohexyl, benzyl, methylbenzyl, chlorobenzyl, bromobenzyl or nitrobenzyl, and

Y is hydrogen or nitro,

are dyestulfs of similar properties as the last-mentioned class, but atford polyester dyeings of even better fastness to sublimation. Optimal results are obtained with the dyestuifs of Formula III in which Y is nitro in 4-position and the ester radical is in 3-positionl Blue to green-blue shades are obtained by using these dyestuffs on cellulose acetate and polyester fibers.

The compounds of the formula V) wherein:

p is an integer ranging from 1 to 2,

X represents either a chlorine or, preferably a bromine atom,

Y represents from one to two chlorine, bromine or hydrogen atoms, and

Y represents chlorine, bromine or preferably nitro,

wherein m is an integer ranging from 0 to 3,

X is either chlorine, or, preferably, bromine,

R is phenyl substituted with from '2 to 5 halogen atoms,

and preferably with 2 to 3 halogen atoms,

X being a substituent as defined above and in being an integer from 0 to 3 inclusive with aromatic diazonium compounds, the resulting novel compounds, derivatives of the compounds of Formula VI are resonance hybrids, of which Formula VI covers the limit electron configurations, as described by Ernest Merian in Chemie der Aminonaphthochinone (Chemia 13, pages 181-212 (1959)), and are referred to in this specification and the appended claims for the sake of brevity as naphthoxidines. The compounds of Formula VI may be further substituted at the naphthalene nucleus and/or one to three of the hydrogen atoms bound to the naphthalene nucleus, can be substituted as described hereinbefore.

Naphthoxidines which are usable as starting materials in the last-mentioned process can be further substituted at the naphthalene nucleus in the 2-, 3-, 6-, or 7- position and at the nitrogen atoms linked to the 1- and/or 5-position. Halogen atoms and/or lower alkyl groups such as chlorine or, preferably, bromine, lower alkyl groups such as methyl, ethyl, n-propyl, isopropyl groups, can be present as substituents of the naphthalene nucleus.

The substitution of a free hydrogen atom, bound to the naphthalene nucleus of naphthoxidine, by the radicals of a diazonium salt wtih cleavage of the nitrogen of the NEN group of the latter is very unexpected, for naphthalene derivatives such as 1-hydroxy-amino-naphthalene coupled with diazonium salts with formations of an azo bridge --N=N-.

The naphthoxidines used as starting materials in the said process fail to show the typical quinone reaction of, for instance, benzoor naphthoquinone. Furthermore, the known arylated benzoor naphthoquinones are relatively unstable due to their pronounced quinone character and are unsuited for use as dyestuffs.

Ring substituted arylated iminobenzoquinones and iminonaphthoquinones have never been produced prior to the present invention, to the best of our knowledge.

Aromatic diazonium compounds which are suitable as reactants in the process for making the compounds used according to the present invention are those of carbo cyclic as well as those of heterocyclic, mono-or bicyclic radicals which retain their aromatic character even in strongly acid solutions, and are of the formula [R-I IEN]X (VII) wherein X is a suitable anion such as 01-, NO;,, 80 HCOO and the like. The nature of the anion is not critical, one of the substituted phenyl radicals defined hereinbefore in Formulas I to V.

The naphthoxidines which may be substituted as defined above, and which are suitable for use in the process for making the compounds to be used according to the invention, are known or can be obtained by methods known per se, for example, from 1,5-dinitronaphthalenes substituted in the 2-, 3-, 6- or 7-position, by partial reduction with sulfur sesquioxide.

In this reaction, from one to two moles, or even an excess over the latter amount, but preferably one mole of diazonium compounds is caused to react with one mole of the starting naphthoxidine at a temperature within the range of 15 and 50 C., whereby an equivalent amount of nitrogen is split off and the aromatic radical corresponding to the diazonium compound enters at a free B-position of the naphthalene nucleus.

More than one, and preferably two diazonium salt radicals R can be introduced into the naphthalene nucleus of the starting naphthoxidines, if the radical R is an active, strongly negatively substituted R and also R with two to five of the halogen substituents of (I) (2.) supra.

Compounds used according to the invention having a further substituted naphthalene radical can be obtained by converting by reduction and/or oxidation, {it-substituted, in particular halogenated naphthalene compounds having suitable substitutents in at least two pi-positions, into naphthoxidines and then reacting these with diazonium compounds. However, unsubstituted naphthoxidines can also be treated by known methods with electrophilically substituting agents and then reacted with aryl diazonium compounds. Finally, the novel naphthoxidines arylated at the naphthalene nucleus by reaction with diazonium compounds can also be modified for example, can be electrophilically substituted and, particularly, halogenated at the naphthalene nucleus; they can also be hydrolyzed at the nitrogen atom.

The conditions for the reaction producing the compounds which are useful according to the invention can be modified within wide margins. Both water or aqueous mineral acid as well as inert organic solvents, preferably those having high solubilizing properties such as dioxan or dimethyl formamide can be used as reaction media. The naphthoxidines can be reacted both in their free form as well as in the form of a metal halide, e.g. metal chloride or metal bromide adduct. Zinc halide adducts, for example the easily isolated zinc chloride double salt of naphthoxidine can be used in an organic solvent; in the preferred method, the aqueous sulfuric acid solution or suspension of the naphthoxidine is used which results from the production of the naphthazarine intermediate product (see Merian supra) in the usual way from 1,5-dinitronaphthalene.

The temperature and duration of the reaction depend to a considerable extent on the nature of the diazonium compound used. Generally, active electrophilically substituted diazonium compounds react considerably more quickly than the less active nucleophilically substituted aryl diazonium compounds. As mentioned above, the reaction takes place in a temperature range between 15 and 50 C. and higher, but without causing hydrolization of the desired end products and/or materials. The preferred temperature range is from to +25 C. and even +30 C. and the average duration of the reaction is about 6 to 24 hours. The reaction medium can be strongly acid to weakly alkaline; an acid medium of a pH smaller than 2 is preferred because of its more general applicability to all starting naphthoxidines. In a commercially preferred mode the reaction medium should contain at least about 20% by weight of water. It is also possible, in certain cases, to add the diazonium salt which has been isolated by filtration and optionally dried, to the naphthoxidine starting compound which has been at least partly dissolved in water or in a suitable, inert organic solvent.

The diazonium salt may also be added to the, preferably aqueous, naphthoxidine solution or suspension, in the form of the acid aqueous diazotation solution in which the diazonium salt has been produced in situ.

The reaction products are isolated in the usual way and are purified if necessary by recrystallization or chromatographic adsorption. Further substitution, for example by halogenation or hydrolysis, is performed by known methods.

The aryl naphthoxidines according to the invention are black-blue to green-black glittering crystalline substance which, in a finely distributed suitable preparation with dispersing agents, dye cellulose acetate, wool, synthetic polyamides or polyesters, either without or after an optional further treatment, e.g. halogenation, in violet, blue to green shades.

Storable compositions for the preparation of aqueous dispersions for the disperse dyeing of polyester fibers and foils, consist densation product or lignin sulfonate or a mixture of both.

The aforesaid naphthalene sulfonic acidformaldehyde condensation products are produced from naphthalene sul fonic acid and formaldehyde in a weight ratio of about 10:1 to 14:1 under conventional condensation conditions. Mixtures of these condensation products with lignin sulfonate can be of random proportions. An anion-active wetting agent such as hydrophilic higher alkylbenzene sulfonates wherein alkyl is of about 10 to 18 carbon atoms, can be added in amounts of about 0.1 to 10% calculated on the total weight of the storable composition.

The following, non-limitative, examples further illustrate the invention. Parts are given therein as parts by weight and the temperatures are in degrees centigrade.

EXAMPLE 1 21.8 parts of 1,5-dinitronaphthalene are reduced in the known manner with sulfur sesquioxide in sulfuric acid to naphthoxidine. The sulfur which precipitates is removed from the solution of the reduction product in sulfuric acid by filtration. The filtrate is then slowly poured into water and ice while stirring well.

The aqueous hydrochloric acid solution of the diazonium compound resulting from diazotation of 17.8 parts of 2,4-dichloro-aniline is added dropwise within about 30 minutes to the blue-violet solution or suspension of naphthoxidine obtained as described above. Foaming ensues and nitrogen is split off. The reaction is completed in about 16 hours at 25. The precipitated crude product is filtered off under suction, washed with water and, to purify the same, it is stirred into about 1000 parts of water and sodium hydroxide solution is added until the pH is about 12 to 13. The suspension is stirred for 2 hours at room temperature and then the precipitate is filtered off. After washing the blue-black residue with water, it is dissolved in 500 parts of boiling ethanol and any undissolved impurities are filtered off from the solution. The alcoholic solution is evaporated to dryness. A glittering, blue-black crystalline powder is obtained which melts at 208-210 on decomposition. '111 ethanol it dissolves with an intensive 25 pure reddish-blue color. Its composition corresponds to the formula NH o In aqueous dispersion, the substance dyes cellulose diand tri-acetate and also polyester fibers in reddish-blue shades which have very good wet and light fastness properties.

By using, in the above example, the diazonium compounds from the amines given in the following Table I, which amines are used in amounts which are equimolar to the amine used in the example and otherwise following the same procedure, then correspondingly substituted derivatives are obtained which have similar properties.

TAB LE I Shade of dyeing with corresponding aryl Ex. compound on cellulose N0. Amine diacetate (2) 1-amino3,4-dichlorobenzene Glcenish-blue. (3) 1-amino-2,5-dichlorobenzene D0. (4) 3-aminobenzene-1-N,N-diethyl-sultonyl Do. (5). taminobenzene methylsulfone. Do. (6) kaminobenzoic acid ethyl ester Rcddish-blue (7) l-aminoAmitrobenzene Greenish-blue (8)- l-amino-B-nitrobenzene. Reddish-bluc (9) 1-amino-2-nitrobenzene D0. (10) Lamina-2,5-dhnethyl-4-nltrobenzene Blue. (11) l-amino2-chloro-4-nitrobenzene Greenish-blue. (12) 1-amino-2-b romo-4-nitrobenzene D 0. (13) l-amlno-4-ehloro-2-nitrobenzene o. (14) l-arnin0-2,4-dibromobenzene Reddish-blue (15) 1-amino-2,4-difiuorobenzene o. (16). 1-aminophenylA-methylketone. Grecnish-blue. (17) 4-amino-d1pheny1ketone Reddlshblue.

EXAMPLE 18 21.8 paths of 1,5-dinitronaphthalene are reduced in sulfuric acid with sulfur sesquioxide to naphthoxidine and the solution is diluted with ice water as described in Example 1.

A solution of the diazonium sulfate from 21.6 parts of 2,4,5-trichloro-l-aminobenzene is added dropwise, Within about 1 hour while stirring, to the ice cold sulfuric acid aqueous solution of the naphthoxidine. After stirring for 18 hours at 10 to 15 the crude product, which has formed with development of nitrogen, is filtered off and purified as described in Example 1. A blue-black glittering product which dissolved in ethanol with a pure greenish-blue color is obtained. It is obtained in pure form by chromatographic adsorption when it then melts at 196-198 on decomposition.

Elementary analysis corresponds to the formula I NH o Found (percent): C, 52.25; H, 2.46; Cl, 28.96; N, 7.63. Calculated (percent) C, 52.21; H, 2.36; Cl, 28.94; N, 7.44.

Dispersed in water in the usual Way, the dyestutf produces pure greenish-blue dyeings on acetate silk or polyester fibers. The d'yeings are fast to wet and light. The drawing power of the dyestuff is remarkably good.

If, in the above example, instead of the diazonium compound from 21.6 parts of 2,4,5-trichloro-l-aminobenzene, diazonium compounds from corresponding amounts of the amines given in the following Table II are used, and otherwise the same procedure is followed, then blue dyestuffs having similar properties are obtained.

EXAMPLE 28 21.8 parts of 1,5-dinitronaphthalene are reduced to naphthoxidine in the usual way with sulfur sesquioxide in 185 parts of sulfuric acid. Excess sulfur is removed by filtration of the sulfuric acid solution of the reaction product and the filtrate is diluted with 300 parts of ice while cooling. A diazonium sulfate solution, obtained by diazotisation of 20 parts of 2-nitro-5 aminobenzoic acidn-butyl ester, dissolved in parts of concentrated sulfuric acid while cooling, is added dropwise to this dilute solution of the naphthoxidine at a temperature of 15 to 20 within about 4 hours. After stirring for another 3 hours, during which time the nitrogen development decreases, the reaction mass is diluted with 1500 parts of ice and water. The precipitated crude product is filtered off, washed with Water, dilute sodium carbonate solution and again with water and dried. A difiicultly soluble, black impurity is removed by extraction with 500 parts of boiling ethanol. A blue-black glittering dyestutf is obtained which dissolves in ethanol with an intensively pure blue color. It is obtained in pure form by recrystallization or chromatographic adsorption on aluminum oxide, and it corresponds to the formula It dyes cellulose acetate and polyester fibers from a suitable aqueous dispersion in pure blue shades which have good fastness properties, in particular very good fastness to sublimation on polyester material.

If in the process described in the above example, a mixture of 200 parts of glacial acetic acid and 70 parts of concentrated hydrochloric acid is used for the diazotisation instead of the 90 parts of sulphuric acid, then a. somewhat higher yield of the same dyestuff is obtained.

If in the above example, with otherwise the same procedure, the diazonium compounds from equimolecular 27 amounts of the amines given in the following Table III are used, then correspondingly substituted derivatives having similar properties are obtained.

15.2 parts of bromine are added. The reaction mixture is refluxed for 2 hours. The solution obtained is washed neutral with water and the chloroform is distilled off.

1-amino-2,5-dichloro-4-nitro-benzene D0. 1-amin0-3-nitr0benzene snlfonie acid diethylamide 1-amino-2,4,5-trichlorobenzene. l-amino-Z,3,4-trichlorobenzene.- 1-aminoA-ehloro-B-trifluoromethyl-benzene 2-nitro-5amino-benzoic acid-benzyl ester D 2-nitro-5amino-benzoie acid-Z-methylbenzyl ester D 2-nitro-5-amino-benzoic aeid-4-ch10robenzyl ester Do. (18)..- 2-nitro-5-amino-benzoic acid-4-bromobenzyl ester Do. (19 2-nitro-5-amino-benzoic acid-tnitrobenzyl ester Do. (20)..- 4-aminobenzene-sulfonic aeid-monoethylamide D0.

EXAMPLE 29 10.4 parts of dibromo naphthoxidine, obtained as described in German Pat. No. 841,314, are dissolved in 200 parts of dimethyl formamide. The diazonium chloride solution from 4.94 parts of 4-nitroaniline is added dropwise to the solution within 1 hour at a temperature between 0 and 10. Nitrogen is developed. After stirring for 6 hours at to the solution is diluted with water, the product which precipitates is filtered off and washed. It is purified by recrystallization from ethanol. In polar organic solvents the reaction product dissolves With a green-blue color; the color is considerably more green than that of the starting material. As dispersion dyestufr, the new compound dyes synthetic fibers such as cellulose acetate or polyester fibers in very pure green-blue shades of good color strength.

Similar dyestuffs are obtained if, in the above example, the reaction components are replaced by equivalent amounts of the starting materials given in the following Table IV.

The brominated dyestuif, which is obtained in a pure form in the usual way, e.g. by recrystallizing or adsorption on an aluminum oxide column; corresponds to the 35 formula From a suitable aqueous dispersion, it dyes cellulose acetate and polyester fibers in pure blue shades which have very good fastness properties. It has good drawing power.

If in the above example, instead of the 26.8 parts of end product according to Example 1, equivalent amounts TAB LE IV Arylated product Naphthoxidine Amine for diazonium shade of dyeing N0. component component on polyester (1) 3,7-dibromonaphthoxidine 1-amino-2A-dieh1orobenzene Greenish-blue.

do 1-amin0-2,4-dibromob enzene D0. (3) do l-amino-2,4,5-trichloro-benZene Do.

l-amino-2-ehloro-4-nitro-benzene- Green-blue.

0 Q. l-arnmo 2 5 dichloro-4-nitrobenzene. o. (6) 3-bromo-naphthoxidiuel-aminol0ro-4-nitrobenzene- Greenish-blue. (7) 2-chloro-naphthoxidine 1-amino-4-mtrobcn zene o. (8) 2,6-dich1oro-naph thoxid ine 1-amin0-2,4, 5-tri-cl11oro-b enzene- Green-blue. (9) 3,7-dibromo-naphthoxidine 1-amino-2-br0m0-4-nitrob enzene D o. (10) do 3-amino-6-nitrob enzoic acid-n-butylester Do EXAMPLE 30 26.8 parts of the end product obtained according to of the arylated naphthoxidine in the following Table VI are used, then dyestuffs having similar properties are ob- Example 1 are dissolved in 300 parts of chloroform and tained.

(2)-..- 2,5-dichlorophenyL- (3)--.- 3,4-dichlorophenyL- (4)-.-. 2,4,5-trichloropheny1 (5)-..- 3,4,5-trich1orophenyL- (6).... 2,4-dibromophenyL (7).- 2,5-dibromophenyl (8) 4-nitrophenyl o. Greenish blue.

(9) 2-ohloro-4-nitrophenyl Do (10).-- 4-chloro-2-nitropheny1 D0. (11)... 2,5-dichloro-4-nitrophenyl Do. (12)... 2,6-dibrorno-4-nitrophenyl Do. (l3) 4-carboethoxyphenyl Reddish blue (14)-.- 2-bromo-4-nitro-phenyl- Blue-green.

EXAMPLE 31 If the procedure given in the Example 30 is followed but instead of 15.2 parts, 30.4 parts of bromine are used, then dyestufis having similar properties and a somewhat more green shade are obtained. Their composition corresponds to the formula:

Chlorine-containing blue dyestuffs are obtained by the above method if the bromine is replaced by the equivalent amount of sulfuryl chloride.

EXAMPLE 32 '2 parts of the dyestulf produced according to Example 12 are dispersed in 4000 parts of water. 12 parts of the sodium salt of o-phenylphenol and 12 parts of diammom'um phosphate are added to this dispersion. 100 parts of terephthalic acid polyglycol ester yarn are dyed for 1% hours at 95-98". The dyeing is rinsed and after-treated With dilute sodium hydroxide solution and a dispersing agent. In this way a greenish-blue dyeing is obtained which is fast to washing, sublimation and light.

If, in the above example, the 100 parts of polyester yarn are replaced by 100 parts of cellulose triacetate fabric, dyeing is performed under the conditions given and the dyeing is then rinsed with Water, then a blue dyeing is obtained which is distinguished by a high degree of wet and light fastness.

EXAMPLE 33 2 parts of the dyestuif obtained according to Example 30 Table VI No. 9 are finely suspended in 2000 parts of water containing 4 parts of a synthetic dispersing agent in a pressure dyeing apparatus. The pH of the dye bath is adjusted to 6.0 to 6.5 with acetic acid. 100 parts of terephthalic acid polyester fabric are introduced at 50, the bath is heated within 30 minutes to 130 and dyeing is performed for 50 minutes at this temperature. The dyeing is rinsed, soaped and dried. A blue dyeing of pure shade is obtained which is fast to Washing, light and very good sublimation.

30 EXAMPLE 34 2 parts of the dyestuif No. 4 in Table VI (Example 31) are finely suspended in 3000 parts of water containing 6 parts of synthetic dispersing agent. 100 parts of cellulose acetate fabric are introduced at 30-40, the temperature is raised within 30 minutes to and dyeing is performed at this temperature for 50 minutes. The blue dyeing obtained is rinsed and dried. It has very good fastness to water, Washing and light as well as remarkable fastness to industrial fumes, especially burnt gas fumes.

EXAMPLE 35 A storable dyestuifdispersant mixture is prepared by intimately mixing by grinding together and subsequently atomizing a mixture of (a) 1 part of the dyestufi No. 7 of Table III prepared according to Example 28, 1 to 3 parts of a synthetic dispersing agent, naphthalene sulfonic acid-formaldehyde condensation product containing the aforesaid components in a ratio of 12:1 by weight,

(b) 1 part of the dyestuif No. 14 of Table VI, prepared according to Example 31, 1 to 3 parts of lignin sulfonate, sold as Artisol 2.

(c) a mixture of 1 part of the dyestufi No. 9 of Table VI prepared according to Example 31, 1 part of a synthetic dispersing agent, naphthalene sulfonic acid-formaldehyde condensation product containing the aforesaid components in a ratio of 12:1 by weight, 1 part of lignin sulfonate, sold as Artisol 2.

From the above storable compositions, dye-baths for disperse dyeing of polyester fibers can be prepared by adding water and, if desired, a wetting agent.

EXAMPLE 36 A storable dyestutf-dispersant mixture is prepared by intimately mixing by grinding together and subsequently atomizing a mixture of 1 part of the dyestuif of Example 28,

1 to 3 parts of lignin sulfonate, sold as Artisol 2,

0.01 to 0.5 parts of dodecyl benzene sulfonate as wetting agent.

Such storable mixtures as described in Examples 35 and 36 may also be in the form of pastes containing about 1 to 3 parts of water obtained by wet grinding the aforesaid ingredients.

In a similar, storable dystntf dispersant mixtures of equally good properties can be produced with other dyestuffs described in Examples 131.

We claim:

1. A process for the production of arylated naphthoxidines, comprising (1) mixing to react with each other at a temperature between -15 and +50 C. in an acid to weakly alkaline medium (a) a naphthoxidine of the formula wherein each X represents a member selected from the group consisting of hydrogen, chlorine, bromine, lower alkyl and phenylamino, at least one X being hydrogen and not more than one X being phenylamino, and, per mol thereof,

31 (b) at least one mol of a diazonium salt of the formula wherein A- is an anion and R is the radical of a mono-to bicyclic aromatic compound, which radical retains its aromatic electron configura tion even in strongly acid medium, and the amino-substituted analog of which is diazotizable, in solvent inert to the reactants and the reaction product;

and recovering the resulting naphthoxidine substituted in at least one B-position of its naphthalene nucleus with said radical R.

2. A process as described in claim 1, wherein the reaction medium has a pH smaller than 2, and contains at least 20% by weight of water.

3. A process as described in claim 1, wherein the temperature of the reaction medium is from about to 30 C.

4. A process as described in claim 1, wherein the solvent is water-diluted sulfuric acid.

5. A process as described in claim 1, wherein the starting naphthoxidine is substituted in ,B-position at its naphthalene nucleus with from one to three members selected from the group consisting of halogen of an atomic weight of maximally 80, lower alkyl and phenylamino, at least one fi-position remaining unsubstituted.

6. A process as described in claim 1, wherein R is a phenyl radical.

7. A process as described in claim 1, wherein from one to two mols of the diazonium salt are added.

8. A process for the production of arylated halogenated naphthoxidine, comprising (I) mixing to react with each other at a temperature between 15 and +50 C. in an acid to weakly alkaline medium (a) a naphthoxidine of the formula wherein each X represents a member selected from the group consisting of hydrogen, chlorine, bromine, lower alkyl and phenylamino, at least 11 +1 Xs being hydrogen and not more than one X being phenylamino, n ranging from 1 to 2, and per mol thereof,

(b) about It mols of a diazonium salt of the formula where A- is an anion and R is the radical of an aromatic compound having from Oneto two carbocyclic rings, which radical retains its aromatic electron configuration even in strongly acid medium, and the amino-substituted analog of which is diazotizable, in solvent inert to the reactants and the reaction product,

(11) adding to the latter a halogenating reactant selected from the group consisting of bromine and sulfurylchloride, thereby halogenating at least one to all of the remaining free ,B-positions of the arylated naphthoxidine resulting from (I), and

(III) recovering the ,H-arylated, B-halogenated naphthoxidine.

9. A process as described in claim 8, wherein the 5- arylated naphthoxidine resulting from step (I) is first 32 isolated from the reaction mixture and then further reacted as defined in step (II).

10. A process for the production of arylated halogenated hemi-naphthazarine or naphthazarine, comprising (I) mixing to react with each other at a temperature between 15 and +50 C. in an acid to weakly alkaline medium (a) a naphthoxidine of the formula wherein each X represents a member selected from the group consisting of hydrogen, chlorine, bromine, lower alkyl and phenylamino, at least one X being hydrogen and not more than one X being phenylamino, and, per mol thereof,

(b) at least one mol of a diazonium salt of the formula wherein A- is an anion and R is the radical of an aromatic compound having from one to two carbocyclic rings, which radical retains its aromatic electron configuration even in strongl acid medium, and the amino-substituted analog of which is diazotizable, in solvent inert to the reactants and the reaction product,

(II) adding to the latter in aqueous medium a hydrolizing agent at 30 to the boiling point of the reaction medium, this temperature depending on the strength and concentration of said hydrolysis agent and the duration of the reaction, thereby converting the ,B-arylated naphthoxidine to the corresponding flarylated naphthazarine derivative in which, dependmg on the acidity of the hydrolysis agent and the applied temperature, from one to both of the two imino groups present in the naphthoxidine nucleus are replaced, depending on the temperature applied, by one to two oxygen atoms.

11. A composition-of-matter of the formula wherein each X is independently a member selected from the group consisting of hydrogen, chlorine, bromine, lower in which formula Y is a member selected from the group consisting of hydrogen, fluorine, chlorine and bromine, and Y is a member selected from the group consisting of hydrogen, chlorine and bromine,

(c) a phenyl radical of the formula in which formula R is a member selected from the group consisting of alkyl with maximally 6 carbon atoms, alkoxyalkyl with maximally 7 carbon atoms, cyclohexyl, 'benzyl, methylbenzyl, chlorobenzyl, bromobenzyl, and nitrobenzyl; and Y is a member selected from the group consisting of hydrogen and nitro; (d) a phenyl radical of the formula in which formula Z is a member selected from the group consisting of CO- and SO and R is a member selected from the group consisting of lower alkyl, phenyl, chlorophenyl and lower alkylphenyl; and

(e) a phenyl radical of the formula in which formula Z has the same meaning as under (d), R is a member selected from the group consisting of hydrogen and alkyl with maximally carbon atoms, and R' is a member selected from the group consisting of hydrogen and alkyl with maximally 5 carbon atoms. 12. A composition-of-matter as defined in claim 11, wherein R is an aryl moiety as defined under (a).

13. A composition-of-matter as defined in claim 11, wherein R is an aryl moiety as defined under (b).

14. A composition-of-matter as defined in claim 11, wherein R is an aryl moiety as defined under (c).

34 15. A composition-of-matter as defined in claim wherein R is an aryl moiety as defined under (d).

16. A composition-of-matter as defined in claim wherein R is an aryl moiety as defined under (e).

17. A composition-of-matter as defined in claim wherein R is the radical of the formula COOCH -CHg-CHz-{llh and each X is hydrogen.

18. A composition-of-matter as defined in claim wherein R is the radical of the formula and each X is hydrogen.

19. A composition-of-matter as defined in claim wherein R is the radical of the formula one X is bromine, and each of the remaining two Xs is hydrogen.

20. A composition-of-matter as defined in claim 13, wherein R is the radical of the formula one X is bromine and each of the remaining two Xs is hydrogen.

21. A composition-of-matter as defined in claim 12, wherein R is the radical of the formula one X is bromine and each of the two remaining Xs is hydrogen.

References Cited UNITED STATES PATENTS 3,422,111 1/ 1969 Bosshard et al. 260-396 LORRAINE A. WEINBERGER, Primary Examiner L. A. THAXT ON, Assistant Examiner U.S. Cl. X.R. 

